US6184187B1ExpiredUtility
Phosphorus compounds and their use as corrosion inhibitors for perfluoropolyethers
Est. expiryApr 7, 2018(expired)· nominal 20-yr term from priority
C10M 2223/02C10M 2213/0623C10M 2213/043C07F 9/091C10N 2030/12C10N 2040/08C10M 2223/063C07F 9/4006C07F 9/3211C07F 9/5004C10M 2223/065C10M 2213/0606C07F 9/4816C23F 11/1673C10M 2223/061C10M 2223/043C10M 137/02C10N 2050/10C10M 2223/049C10M 2213/00C10M 2223/06C10M 2225/00C10M 2223/04C10M 2223/042C10M 137/12C10M 2223/10C07F 9/46C07F 9/4075C10M 169/04C07F 9/5304C10M 2225/02C10M 2213/023C07F 9/12Y10T428/31544C10M 107/38
90
PatentIndex Score
71
Cited by
15
References
29
Claims
Abstract
Novel phosphorus compounds are effective corrosion inhibitors for perfluoropolyether lubricating oils and greases, and hydraulic fluids.
Claims
exact text as granted — not AI-modifiedWhat is claimed is:
1. A perfluoropolyether oil or grease containing 0.1 to 10% by weight of an aryl phosphorus compound selected from the group consisting of:
A. A perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compound selected from the group consisting of partially esterified aryl phosphates, aryl phosphonates, and salts thereof, containing either (i) a mono- or poly-alkylene oxide linking group between the phosphorus and a fluorocarbon group, or (ii) no linking group between the phosphorus and fluorocarbon group;
B. Asymmetrical perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compounds being either (i) aryl phosphites or phosphates containing a mono- or poly-alkylene oxide linking group between the phosphorus and a perfluoroether group, or (ii) aryl phosphines, phosphinites, phosphonites, phosphine oxides, phosphinates or phosphonates with no linking group between the phosphorus and a fluorocarbon group;
and combinations thereof wherein said salt is selected from the group consisting of alkali metal salts, alkaline earth metal salts, ammonium salts, and combinations thereof.
2. The perfluoroether oil or grease of claim 1 containing 0.1 to 3% by weight of at least one partially esterified aryl phosphate, aryl phosphonate, or salts thereof, containing either (i) a mono- or poly-alkylene oxide linking group between the phosphorus and a fluorocarbon group, or (ii) no linking group between the phosphorus and fluorocarbon group.
3. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [Rf—Y—] (2−x) —P(E)—[O b C 6 R 5 ][OM] x wherein
Y is (CH 2 ) z O(CH 2 CH 2 O) z , in which z is 1 to 4 and z′ is 0, 1 or 2;
x is 0.05 to 1;
E is oxygen or sulfur,
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—O—(CF(CF 3 )CF 2 O) o —(CFXO) d —CFZ—, (2) J 1 —O—(CF 2 CF 2 O) e —(CF 2 O) f —CFZ 1 , (3) J—(CF(CF 3 )CF 2 O) g —(CF 2 CF 2 O) h —(CFX—O) i —CFZ—, (4) J 2 —O—(CF(CF 3 )CF 2 O) j —CF(CF 3 )—, (5) J 3 —O—(CQZ 2 —CF 2 CF 2 —O) k —CQZ 2 —CF 2 —, and (6) J 4 —O—(CF 2 CF 2 O) 1 —CF 2 —;
J is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF 2 Cl, —C 2 F 4 Cl, and —C 3 F 6 Cl;
X is —F or —CF 3 ;
Z is —F, —Cl, or —CF 3 ;
Z 1 is —F or —Cl;
c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;
J 1 is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —CF 2 Cl, and —C 2 F 4 Cl;
e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;
g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
J 2 is —C 2 F, or —C 3 F 7 ;
j is a number such that the molecular weight ranges from 400 to 15,000;
J 3 is selected from the group consisting of —CF 3 , —C 2 F 5 , and —C 3 F 7 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
k is a number such that the molecular weight ranges from 400 to 15,000;
j 4 is —CF 3 , or —C 2 F 5 ; and
l is a number such that the molecular weight ranges from 400 to 15,000.
4. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [Rf′—Y—] (2−x) —P(E)—[O b C 6 R 5 ][OM] x wherein
Y is (CH 2 ) z O(CH 2 CH 2 O) z , in which z is 1 to 4 and z′ is 0, 1 or 2;
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf′ is Z 2 —(CF 2 ) m ;
Z 2 is F, Cl or H; and
m has a value from 2 to 20.
5. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [MO] x [C 6 R 5 O b ]—P(E)—Y—Rf″—Y—P(E)—[O b C 6 R 5 ] (2−x) [OM] x wherein
Y is (CH 2 ) z O(CH 2 CH 2 O) z , in which z is 1 to 4 and z′ is 0, 1 or 2;
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000
X is F or CF 3 ;
Q and Z 2 , equal or different, are —F, —Cl or —H; and
s is a number such that the molecular weight ranges from 400 to 15,000.
6. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [Rf—] (2−x) —P(E)—[O b C 6 R 5 ][OM] x wherein
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—O—(CF(CF 3 )CF 2 O) c —(CFXO) d —CFZ—, (2) J 1 —O—(CF 2 CF 2 O) e —(CF 2 O) f —CFZ 1 , (3) J—(CF(CF 3 )CF 2 O) g —(CF 2 CF 2 O) h —(CFX—O) i —CFZ—, (4) J 2 —O—(CF(CF 3 )CF 2 O) j —CF(CF 3 )—, (5) J 3 —O—(CQZ 2 —CF 2 CF 2 —O) k —CQZ 2 —CF 2 —, and (6) J 4 —O—(CF 2 CF 2 O) 1 —CF 2 —;
J is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF 2 Cl, —C 2 F 4 Cl, and —C 3 F 6 Cl;
X is —F or —CF 3 ;
Z is —F, —Cl, or —CF 3 ;
Z 1 is —F or —Cl;
c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;
J 1 is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —CF 2 Cl, and —C 2 F 4 Cl;
e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;
g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
J 2 is —C 2 F 5 or —C 3 F 7 ;
j is a number such that the molecular weight ranges from 400 to 15,000;
J 3 is selected from the group consisting of —CF 3 , —C 2 F 5 , and —C 3 F 7 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
k is a number such that the molecular weight ranges from 400 to 15,000;
J 4 is —CF 3 , or —C 2 F 5 ; and
l is a number such that the molecular weight ranges from 400 to 15,000.
7. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [Rf′—] (2−x) —P(E)—[O b C 6 R 5 ][OM] x wherein
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf′ is Z 2 —(CF 2 ) m ;
Z 2 is —F, —Cl or —H; and
m has a value from 2 to 20.
8. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [MO] x [C 6 R 5 O b ]—P(E)—Rf″—P(E)—[O b C 6 R 5 ] (2−x) [OM] x wherein
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
X is —F or —CF 3 ;
Q and Z 2 , equal or different, are —F, —Cl or —H; and
s is a number such that the molecular weight ranges from 400 to 15,000.
9. The perfluoropolyether oil or grease composition of claim 1 containing 0.1 to 3% by weight of at least one asymmetrical perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compound being either (i) aryl phosphites or phosphates containing a mono- or poly-alkylene oxide linking group between the phosphorus and a perfluoroether group, or (ii) aryl phosphines, phosphinites, phosphonites, phosphine oxides, phosphinates or phosphonates with no linking group between the phosphorus and a fluorocarbon group.
10. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [Rf—Y—] (3−y) —P(E) a —[O—C 6 R 5 ] y wherein
Y is (CH 2 ) z O(CH 2 CH 2 O) z , in which z is 1 to 4 and z′ is 0, 1 or 2;
E is oxygen or sulfur;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—O—(CF(CF 3 )CF 2 O) c —(CFXO) d —CFZ—, (2) J 1 —O—(CF 2 CF 2 O) e —(CF 2 O) f —CFZ 1 , (3) J—(CF(CF 3 )CF 2 O) g —(CF 2 CF 2 O) h —(CFX—O) i —CFZ—; (4) J 2 —O—(CF(CF 3 )CF 2 O) j —CF(CF 3 )—, (5) J 3 —O—(CQZ 2 —CF 2 CF 2 —O) k —CQZ 2 —CF 2 —, and (6) J 4 —O—(CF 2 CF 2 O) l —CF 2 —;
J is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF 2 Cl, —C 2 F 4 Cl, and —C 3 F 6 Cl;
X is —F or —CF 3 ;
Z is —F, —Cl, or —CF 3 ;
Z 1 is —F or —Cl;
c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5, and the molecular weight ranges from 400 to 15,000;
J 1 is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —CF 2 Cl, and —C 2 F 4 Cl;
e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and, the molecular weight ranges from 400 to 15,000;
g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
J 2 is —C 2 F 5 or —C 3 F 7 ;
j is a number such that the molecular weight ranges from 400 to 15,000;
J 3 is selected from the group consisting of —CF 3 , —C 2 F 5 , and —C 3 F 7 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
k is a number such that the molecular weight ranges from 400 to 15,000;
J 4 is —CF 3 , or —C 2 F 5 ;
l is a number such that the molecular weight ranges from 400 to 15,000;
y is 0.05 to 2; and
a is 0 or 1.
11. The composition of claim 9 wherein said aryl phosphorus compound has the formula of (C 6 R 5 O) 2 —P(E) a —Y—Rf″—Y—P(E) a —(OC 6 R 5 ) 2 wherein
Y is (CH 2 ) z —O(CH 2 CH 2 O) z —, in which z is 1 to 4 and z′ is 0, 1 or 2;
E is oxygen or sulfur;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
X is —F or —CF 3 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
s is a number such that the molecular weight ranges from 400 to 15,000; and
a is 0 or 1.
12. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [Rf] (3−y) —P(E) a —[O b C 6 R 5 ] y wherein
E is oxygen or sulfur;
b is 0 or 1;
Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—O—(CF(CF 3 )CF 2 O) c —(CFXO) d —CFZ—, (2) J 1 —O—(CF 2 CF 2 O) e —(CF 2 O) f —CFZ 1 , (3) J—(CF(CF 3 )CF 2 O) g —(CF 2 CF 2 O) h —(CFX—O) i —CFZ—; (4) J 2 —O—(CF(CF 3 )CF 2 O) j —CF(CF 3 )—, (5) J 3 —O—(CQZ 2 —CF 2 CF 2 —O) k —CQZ 2 —CF 2 —, and (6) J 4 —O—(CF 2 CF 2 O) 1 —CF 2 —;
J is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF 2 Cl, —C 2 F 4 Cl, and —C 3 F 6 Cl;
X is —F or —CF 3 ;
Z is —F, —Cl, or —CF 3 ;
Z 1 is —F or —Cl;
c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;
J 1 is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —CF 2 Cl, and —C 2 F 4 Cl;
e and f are numbers such that the elf ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000; g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
J 2 is —C 2 F 5 or —C 3 F 7 ;
j is a number such that the molecular weight ranges from 400 to 15,000;
J 3 is selected from the group consisting of —CF 3 , —C 2 F 5 , and —C 3 F 7 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
k is a number such that the molecular weight ranges from 400 to 15,000;
J 4 is —CF 3 , or —C 2 F 5 ;
l is a number such that the molecular weight ranges from 400 to 15,000;
y is 0.05 to 2; and
a is 0 or 1.
13. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [Rf′] (3−y) —P(E) a —[O b C 6 R 5 ] y wherein
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf′ is Z 2 —(CF 2 ) m ;
Z 2 is F, Cl or H;
m has a value from 2 to 20;
y is 0.05 to 2; and
a is 0 or 1.
14. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [C 6 R 5 O] 2 —P(E) a —Rf″—P(E) a —[O—C 6 R 5 ] 2 wherein
E is oxygen or sulfur;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
s is a number such that the molecular weight ranges from 400 to 15,000;
X is —F or —CF 3 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
y is 0.05 to 2; and
a is 0 or 1.
15. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [Rf′″—C 6 R 4 —O] (3-u-w) —P(E)—[O b —C 6 R′ 5 ] w [OM′] u wherein
Rf′″ is Rf′ or Rf″;
M′ is an alkali metal, alkaline earth metal, or ammonium;
u and w are the same or different and are between 0 and 1;
R′ is an aryl group;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf′ is Z 2 —(CF 2 ) m ;
m has a value from 2 to 20;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
s is a number such that the molecular weight ranges from 400 to 15,000;
X is —F or —CF 3 ; and
Q and Z 2 , equal or different, are F, Cl or H.
16. A perfluoropolyether oil or grease composition of containing 0.1 to 3% by weight of at least one salts of a partially esterified aryl phosphates having an aryl group between the phosphorus and a fluorocarbon; said aryl phosphorus compound has the formula of [Rf′″—C 6 R 4 —O] (3-u-w) —P(E)—[O b —C 6 R′ 5 ] w [OM′] u wherein
Rf′″ is Rf′ or Rf″;
M′ is an alkali metal, alkaline earth metal, or ammonium;
u and w are the same or different and are between 0 and 1;
R′ is an aryl group;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf′ is Z 2 —(CF 2 ) m ;
m has a value from 2 to 20;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
s is a number such that the molecular weight ranges from 400 to 15,000;
X is —F or —CF 3 ; and
Q and Z 2 , equal or different, are F, Cl or H.
17. A perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compound selected from the group consisting of partially esterified aryl phosphates, aryl phosphonates, and salts thereof, containing either (i) a mono- or poly-alkylene oxide linking group between the phosphorus and a fluorocarbon group, or (ii) no linking group between the phosphorus and fluorocarbon group wherein said salt is selected from the group consisting of alkali metal salts, alkaline earth metal salts, ammonium salts, and combinations thereof.
18. Compounds of claim 17 having the formula of [Rf—Y—] (2−x) —P(E)—[O b C 6 R 5 ][OM] x wherein
Y is (CH 2 ) z O(CH 2 CH 2 O) z , in which z is 1 to 4 and z′ is 0, 1 or 2;
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—O—(CF(CF 3 )CF 2 O) c —(CFXO) d —CFZ—, (2) J 1 —O—(CF 2 CF 2 O) e —(CF 2 O) f —CFZ 1 , (3) J—(CF(CF 3 )CF 2 O) g —(CF 2 CF 2 O) h —(CFX—O) i —CFZ—, (4) J 2 —O—(CF(CF 3 )CF 2 O) j —CF(CF 3 )—, (5) J 3 —O—(CQZ 2 —CF 2 CF 2 —O) k —CQZ 2 —CF 2 —, and (6) J 4 —O—(CF 2 CF 2 O) 1 —CF 2 —;
J is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF 2 Cl, —C 2 F 4 Cl, and —C 3 F 6 Cl;
X is —F or —CF 3 ;
Z is —F, —Cl, or —CF 3 ;
Z 1 is —F or —Cl;
c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;
J 1 is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —CF 2 Cl, and —C 2 F 4 Cl;
e and f are numbers such that the e/f ratio′ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;
g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
J 2 is —C 2 F 5 or —C 3 F 7 ;
j is a number such that the molecular weight ranges from 400 to 15,000;
J 3 is selected from the group consisting of —CF 3 , —C 2 F 5 , and —C 3 F 7 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
k is a number such that the molecular weight ranges from 400 to 15,000;
J 4 is —CF 3 , or —C 2 F 5 ; and
l is a number such that the molecular weight ranges from 400 to 15,000.
19. Compounds of claim 17 having the formula of [Rf′—Y—] (2−x) —P(E)—[O b C 6 R 5 ][OM] x wherein
Y is (CH 2 ) z O(CH 2 CH 2 O) z , in which z is 1 to 4 and z′ is 0, 1 or 2;
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf′ is Z 2 —(CF 2 ) m ;
Z 2 is F, Cl or H; and
m has a value from 2 to 20.
20. Compounds of claim 17 having the formula of [MO] x [C 6 R 5 O b ]—P(E)—Y—Rf″—Y—P(E)—[O b C 6 R 5 ] (2−x) [OM] x wherein
Y is (CH 2 ) z O(CH 2 CH 2 O) z , in which z is 1 to 4 and z′ is 0, 1 or 2;
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
X is F or CF 3 ;
Q and Z 2 , equal or different, are —F, —Cl or —H; and
s is a number such that the molecular weight ranges from 400 to 15,000.
21. Compounds of claim 17 having the formula of [Rf—] (2−x) —P(E)—[O b C 6 R 5 ][OM] x wherein
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—O—(CF(CF 3 )CF 2 O) O —(CFXO) d —CFZ—, (2) J 1 —O—(CF 2 CF 2 O) e —(CF 2 O) f CFZ 1 , (3) J—(CF(CF 3 )CF 2 O) g —(CF 2 CF 2 O) h —(CFX—O) i —CFZ—, (4) J 2 —O—(CF(CF 3 )CF 2 O) j —CF(CF 3 )—, (5) J 3 —O—(CQZ 2 —CF 2 CF 2 —O) k —CQZ 2 —CF 2 —, and (6) J 4 —O—(CF 2 CF 2 O) 1 —CF 2 —;
J is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF 2 Cl, —C 2 F 4 Cl, and —C 3 F 6 Cl;
X is —F or —CF 3 ;
Z is —F, —Cl, or —CF 3 ;
Z 1 is —F or —Cl;
c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;
J 1 is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —CF 2 Cl, and —C 2 F 4 Cl;
e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;
g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
J 2 is —C 2 F 5 or —C 3 F 7 ;
j is a number such that the molecular weight ranges from 400 to 15,000;
J 3 is selected from the group consisting of—CF 3 , —C 2 F 5 , and —C 3 F 7 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
k is a number such that the molecular weight ranges from 400 to 15,000;
J 4 is —CF 3 , or —C 2 F 5 ; and
l is a number such that the molecular weight ranges from 400 to 15,000.
22. Compounds of claim 17 having the formula of [Rf′—] (2−x) —P(E)—[O b C 6 R 5 ][OM] x wherein
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf′ is Z 2 —(CF 2 ) m ;
Z 2 is —F, —Cl or —H; and
m has a value from 2 to 20.
23. Compounds of claim 17 having the formula of [MO] x [C 6 R 5 O b ]—P(E)—Rf″—P(E)—[O b C 6 R 5 ] (2−x) [OM] x wherein
x is 0.05 to 1;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
X is —F or —CF 3 ;
Q and Z 2 , equal or different, are —F, —Cl or —H; and
s is a number such that the molecular weight ranges from 400 to 15,000.
24. Asymmetrical perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compounds being aryl phosphites or phosphates containing a mono- or poly-alkylene oxide linking group between the phosphorus and a perfluoroether group.
25. Compounds of claim 24 having the formula of [Rf—Y—] (3−y) —P(E) a —[O—C 6 R 5 ] y wherein
Y is (CH 2 ) z O(CH 2 CH 2 O) z , in which z is 1 to 4 and z′ is 0, 1 or 2;
E is oxygen or sulfur;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—O—(CF(CF 3 )CF 2 O) c —(CFXO) d —CFZ—, (2) J 1 —O—(CF 2 CF 2 O) e —(CF 2 O) f —CFZ 1 , (3) J—(CF(CF 3 )CF 2 O) g —(CF 2 CF 2 O) h —(CFX—O) i —CFZ—; (4) J 2 —O—(CF(CF 3 )CF 2 O) j —CF(CF 3 )—, (5) J 3 —O—(CQZ 2 —CF 2 CF 2 —O) k —CQZ 2 —CF 2 —, and (6) J 4 —O—(CF 2 CF 2 O) 1 —CF 2 —;
J is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF 2 Cl, —C 2 F 4 Cl, and —C 3 F 6 Cl;
X is —F or —CF 3 ;
Z is —F, —Cl, or —CF 3 ;
Z 1 is —F or —Cl;
c and d are numbers such that the cld ratio ranges from 0.01 to 0.5, and the molecular weight ranges from 400 to 15,000;
J 1 is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —CF 2 Cl, and —C 2 F 4 Cl;
e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and, the molecular weight ranges from 400 to 15,000;
g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
J 2 is —C 2 F 5 or —C 3 F 7 ;
j is a number such that the molecular weight ranges from 400 to 15,000;
J 3 is selected from the group consisting of —CF 3 , —C 2 F 5 , and —C 3 F 7 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
k is a number such that the molecular weight ranges from 400 to 15,000;
J 4 is —CF 3 , or —C 2 F 5 ;
l is a number such that the molecular weight ranges from 400 to 15,000;
y is 0.05 to 2; and
a is 0 or 1.
26. Compounds of claim 24 having the formula of (C 6 R 5 O) 2 —P(E) a —Y—Rf″—Y—P(E) a —(OC 6 R 5 ) 2 wherein
Y is (CH 2 ) z O(CH 2 CH 2 O) z , in which z is 1 to 4 and z′ is 0, 1 or 2;
E is oxygen or sulfiur;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
X is —F or —CF 3 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
s is a number such that the molecular weight ranges from 400 to 15,000; and
a is 0 or 1.
27. Compowuds of claim 24 having the formula of [Rf] (3−y) —P(E) a —[O b C 6 R 5 ] y wherein
E is oxygen or sulfur;
b is 0 or 1;
Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—O—(CF(CF 3 )CF 2 O) c —(CFXO) d —CFZ—, (2) J 1 —O—(CF 2 CF 2 O) e —(CF 2 O) f —CFZ 1 , (3) J—(CF(CF 3 )C 2 O) g —(CF 2 CF 2 O) h —(CFX—O) i —CFZ—; (4) J 2 —O—(CF(CF 3 )CF 2 O) j —CF(CF 3 )—, (5) J 3 —O—(CQZ 2 —CF 2 CF 2 —O) k —CQZ 2 —CF 2 —, and (6) J 4 —O—(CF 2 CF 2 O) 1 —CF 2 —;
J is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF 2 Cl, —C 2 F 4 Cl, and —C 3 F 6 Cl;
X is —F or —CF 3 ;
Z is —F, —Cl, or —CF 3 ;
Z 1 is —F or —Cl;
c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;
J 1 is a fluoroalkyl group selected from the group consisting of —CF 3 , —C 2 F 5 , —CF 2 Cl, and —C 2 F 4 Cl;
e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000; g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
J 2 is —C 2 F 5 or —C 3 F 7 ;
j is a number such that the molecular weight ranges from 400 to 15,000;
J 3 is selected from the group consisting of —CF 3 , —C 2 F 5 , and —C 3 F 7 ;
Q and Z 2 , equal or different, are —F, —Cl or —H;
k is a number such that the molecular weight ranges from 400 to 15,000;
J 4 is —CF 3 , or —C 2 F 5 ;
l is a number such that the molecular weight ranges from 400 to 15,000.
y is 0.05 to 2; and
a is 0 or 1.
28. Compounds of claim 24 having the formula of [C 6 R 5 O] 2 —P(E) a —Rf″—P(E) a —[O—C 6 R 5 ] 2 wherein
E is oxygen or sulfur;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000 selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
s is a number such that the molecular weight ranges from 400 to 15,000;
X is —F or —CF 3 ;
Q and Z 2 , equal or different, are —F, —Cl or —H; and
a is 0 or 1.
29. Salts of partially esterified aryl phosphates having an aryl group between the phosphorus and a fluorocarbon; said salt is selected from the group consisting of alkali metal salts, alkaline earth metal salts, ammonium salts, and combinations thereof and has the formula of[Rf′″—C 6 R 4 —O] (3-u-w)—P(E)—[O b —C 6 R′ 5 ] w [OM′] u wherein
Rf′″ is Rf′ or Rf″;
M′ is an alkali metal, alkaline earth metal, or ammonium;
u and w are the same or different and are between 0 and 1;
R′ is an aryl group;
E is oxygen or sulfur;
b is 0 or 1;
each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;
Rf′ is Z 2 —(CF 2 ) m ;
m has a value from 2 to 20;
Rf″ is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —(CF 2 CF 2 O) n —(CF 2 O) o —CF 2 —, (ii) —(C 3 F 6 O) p —(CF 2 CF 2 O) q —(CFXO) r —CF 2 —, and (iii) —((CQZ 2 )CF 2 CF 2 O) s —CF 2 —CF 2 —;
the units with formulae C 2 F 4 O and CF 2 O are randomly distributed along the chain;
n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;
p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;
s is a number such that the molecular weight ranges from 400 to 15,000;
X is —F or —CF 3 ; and
Q and Z 2 , equal or different, are F, Cl or H.Cited by (0)
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